CN116057108A - Polyamides for textile applications - Google Patents

Polyamides for textile applications Download PDF

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Publication number
CN116057108A
CN116057108A CN202180058270.6A CN202180058270A CN116057108A CN 116057108 A CN116057108 A CN 116057108A CN 202180058270 A CN202180058270 A CN 202180058270A CN 116057108 A CN116057108 A CN 116057108A
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Prior art keywords
polyamide
total
acid
diamine
linear aliphatic
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Inventor
S·卡西亚诺加斯帕尔
T·布里富
J-J·弗拉特
P·丹
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Arkema France SA
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Arkema France SA
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyamides (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Artificial Filaments (AREA)
  • Woven Fabrics (AREA)

Abstract

The present invention relates to linear aliphatic polyamides obtained by polycondensation of at least one linear aliphatic unit selected from the group consisting of: a C6 to C12 α, ω -aminocarboxylic acid, a C6 to C12 lactam and a (Ca-diamine), (Cb-diacid) unit, wherein a represents the number of carbon atoms of the diamine and b represents the number of carbons of the diacid, a and b ranging between 4 and 18, the polyamide having a difference between 35 and 180, expressed in absolute value, between its total acidity and its total basicity, and a total basicity or total acidity strictly less than 35 μeq/g. The invention also relates to a method for the production thereof and to the use thereof in the textile sector.

Description

Polyamides for textile applications
Technical Field
The present invention relates to polyamides with improved textile properties. The invention also relates to a method for the production thereof and to the use thereof for producing textile materials.
Background
The use of synthetic textile fibres based on polyamides has been known for many years. Textiles include fibrous mats (dressing), filters, felts), coarse sand (dressing), yarns (sewing threads, knitting threads, braiding threads), (flat, cylindrical, fully formed or shaped) knitted fabrics, fabrics (traditional, jacquard, multi-faceted), double-sided, multiaxial, 2.5D, 3D fabrics) and more. Innovations in this area often occur, for example, in sportswear, which allows sweat to be more easily removed. Innovations in fiber dyeing ability have recently also emerged. Thus, when treating textile materials to impart a particular color, shape, or specific treatment, such as an antimicrobial treatment or a flame retardant treatment, the textile materials may be subjected to multiple treatment steps and/or more rigorous (tougher) treatments, rendering the fibers more fragile.
Furthermore, in view of current climate problems, textile materials are sought that can be fully recycled.
Thus, new materials are being sought that are both thermally and mechanically stronger and have the advantage of being recyclable.
Disclosure of Invention
The present invention relates to linear aliphatic polyamides obtained by polycondensation of at least one linear aliphatic unit selected from the group consisting of: a C6 to C12 α, ω -aminocarboxylic acid, a C6 to C12 lactam and a (Ca-diamine), (Cb-diacid) unit, wherein a represents the number of carbon atoms of the diamine and b represents the number of carbon atoms of the diacid, a and b being between 4 and 18, the polyamide having
-the difference between its total acidity and its total basicity expressed in absolute value between 35 and 180, and
total basicity or total acidity strictly less than 35 μeq/g.
The invention also relates to a process for preparing the polyamide.
The invention also relates to a composition comprising said polyamide.
Finally, the invention relates to textile materials made from said polyamide or from a composition containing it.
The polyamide according to the invention is observed to exhibit excellent heat stability properties and excellent mechanical properties. It also has excellent rheological stability. This means that it changes very little when hot. In other words, when it is melted to prepare a filament (fileent), its viscosity change is very small. This property is highly sought by the manufacturer. In fact, for example, if the production line has to be stopped for any reason (such as a fault in the production line), it can be restarted without losing material during the production process. The molten material will change little or no during the interruption and the filaments produced during the stop will have the desired properties. No loss is recorded.
Furthermore, the polyamide according to the invention has the following advantages: it may be recycled. Its rheological stability allows it to be easily remelted and reused for preparing new filaments. The properties of the remelted polyamide are very similar, if not identical, to those of the first-melted polyamide.
Detailed Description
Other features, characteristics, subjects and benefits of the present invention will appear even more clearly upon reading the following description.
The nomenclature used to define polyamides is described in ISO Standard 1874-1:2011 "plasma-Mateiaux Polyamides (PA) pour moulage et extrusion-part 1:design", especially at page 3 (tables 1 and 2), and is well known to those skilled in the art.
It is also noted that the expressions "between … … and … …" and "from … … to … …" used in this specification must be understood to include each indicated limit.
The word "polyamide" encompasses both homo-and copolyamides.
In this specification of the present invention, it is understood that:
"textile material" or "textile" means any material made of fibers or filaments and any material forming a porous membrane (membrane) characterized by a ratio of length to thickness of at least 300;
"fiber" means any synthetic or natural material characterized by a length/diameter ratio of at least 300;
"filament" means any fiber of infinite length.
The invention will now be described in more detail in the following description in a non-limiting manner.
Polyamide
The polyamide according to the invention is obtained by polycondensation of at least one linear aliphatic unit chosen from: c6 to C12 α, ω -aminocarboxylic acid, C6 to C12 lactam and (Ca-diamine), (Cb-diacid) units, wherein a represents the number of carbon atoms of the diamine and b represents the number of carbons of the diacid, a and b being between 4 and 18.
The polyamide according to the invention can be obtained by polycondensation of at least one lactam selected from the group consisting of pyrrolidone, 2-piperidone, heptanolactam (enantholactam), octalactam (caprolactam), pelargolactam (pelargolactam), decalactam (decanolactam), undecanolactam (undecanoactam) and laurolactam.
The polyamide according to the invention is also obtainable by polycondensation of at least one amino acid selected from the group consisting of 10-aminodecanoic acid (denoted 10), 11-aminoundecanoic acid (denoted 11), 12-aminododecanoic acid (denoted 12).
The polyamide is obtainable by polycondensation of at least one unit satisfying the formula (Ca diamine), (Cb diacid), wherein a represents the number of carbon atoms of the diamine and b represents the number of carbons of the diacid, a and b being between 4 and 18.
The units (Ca diamine) may be selected from butanediamine (a=4), pentanediamine (a=5), hexanediamine (a=6), heptanediamine (a=7), octanediamine (a=8), nonanediamine (a=9), decanediamine (a=10), undecanediamine (a=11), dodecanediamine (a=12), tridecanediamine (a=13), tetradecanediamine (a=14), hexadecanediamine (a=16) and octadecanediamine (a=18).
The units (Cb diacid) may be selected from succinic acid (b=4), glutaric acid (b=5), adipic acid (b=6), pimelic acid (b=7), suberic acid (b=8), azelaic acid (b=9), sebacic acid (b=10), undecanedioic acid (b=11), dodecanedioic acid (b=12), tridecanedioic acid (basicylic acid) (b=13), tetradecanedioic acid (b=14), hexadecanedioic acid (b=16) and octadecanedioic acid (b=18).
According to a preferred embodiment, the polyamide according to the invention is a homopolyamide. The homopolyamide can be obtained by polycondensation as follows: lactam, amino acid or unit (Ca diamine), (Cb diacid), wherein Ca and Cb are as defined above.
Preferably, the polyamide according to the invention is a linear aliphatic homo-polyamide obtained by polycondensation of one linear aliphatic unit selected from the group consisting of: a C6 to C12 α, ω -aminocarboxylic acid, a C6 to C12 lactam and a (Ca-diamine), (Cb-diacid) unit, wherein a represents the number of carbon atoms of the diamine and b represents the number of carbon atoms of the diacid, a and b being between 4 and 18, the polyamide having
-the difference between its total acidity and its total basicity expressed in absolute value between 35 and 180, and
total basicity or total acidity strictly less than 35 μeq/g.
Even more preferably, the polyamide according to the invention is a linear aliphatic homo-polyamide obtained by polycondensation of one linear aliphatic unit selected from the group consisting of: a C8 to C12 α, ω -aminocarboxylic acid, a C8 to C12 lactam and a (Ca-diamine), (Cb-diacid) unit, wherein a represents the number of carbon atoms of the diamine and b represents the number of carbon atoms of the diacid, a and b being between 8 and 12, the polyamide having
-the difference between its total acidity and its total basicity expressed in absolute value between 35 and 180, and
total basicity or total acidity strictly less than 35 μeq/g.
Advantageously, the homopolyamide according to the invention is selected from PA11, PA12, PA1010, PA1012, more particularly PA11.PA11 is obtained by polycondensation of 11-aminoundecanoic acid. PA12 is obtained by polycondensation of laurolactam. PA1010 is obtained by polycondensation of decanediamine and decanedioic acid. PA1012 is obtained by polycondensation of decanediamine and dodecanedioic acid.
PA11 has the advantage of being made from raw materials of vegetable origin. Plant material can be grown in large quantities in most areas of the world and is biobased, as desired. The biobased raw material is a natural resource (whether animal or plant) whose stock is reconfigurable on the human scale in a short time. In particular, such inventory must be able to be updated as quickly as it is consumed.
The basic raw material of PA11 is castor oil extracted from castor oil plants (common ricin), in particular from castor seeds. PA11 is obtained by polycondensation of 11-aminoundecanoic acid.
According to another embodiment, the polyamide is a linear aliphatic copolyamide of formula A/B obtained by polycondensation of at least two monomers of different structure
Wherein the method comprises the steps of
The unit A is selected from the group consisting of C6 to C12 alpha, omega-aminocarboxylic acids, C6 to C12 lactams and (Ca-diamine), (Cb-diacid) units, wherein a represents the number of carbon atoms of the diamine and b represents the number of carbons of the diacid, a and b being between 4 and 18,
the unit B is selected from the group consisting of C6 to C12 alpha, omega-aminocarboxylic acids, C6 to C12 lactams and (Ca-diamine), (Cb-diacid) units, wherein a represents the number of carbon atoms of the diamine and B represents the number of carbons of the diacid, a and B being between 4 and 18,
a and B are different structures, the polyamide having
-the difference between its total acidity and its total basicity expressed in absolute value between 35 and 180, and
total basicity or total acidity strictly less than 35 μeq/g.
Preferably, the unit a is selected from C8 to C12 α, ω -aminocarboxylic acid, C8 to C12 lactam and (Ca-diamine), (Cb-diacid) units, wherein a represents the number of carbon atoms of the diamine and B represents the number of carbons of the diacid, a and B being between 8 and 12, and the unit B is selected from C8 to C12 α, ω -aminocarboxylic acid, C8 to C12 lactam and (Ca-diamine), (Cb-diacid) units, wherein a represents the number of carbon atoms of the diamine and B represents the number of carbons of the diacid, a and B being between 8 and 12.
Preferably, the polyamide is selected from the group consisting of PA11/1010, PA11/1012, PA11/1212, PA1010/1012, PA1010/1212, PA12/1010, PA 12/1012, PA12/1212.
Total acidity and total basicity
The polyamide according to the invention has a difference between 35 and 180 expressed in absolute value between its total acidity and its total basicity.
For the purposes of the present invention, the difference expressed in absolute terms means the result of subtracting the values of total acidity and total basicity, irrespective of the sign.
Preferably, the difference between the total acidity and the total basicity, expressed in absolute value, is between 40 and 110.
The polyamide according to the invention also has a total alkalinity or total acidity strictly less than 35. Mu. Eq/g.
Acidity and basicity were measured by potentiometry (potentiometry).
Acidity was measured according to the following method. A sample of polyamide was dissolved in benzyl alcohol. Next, the sample was quantified by potentiometry (dose) with 0.02N tetrabutylammonium hydroxide solution.
Alkalinity was measured according to the following method. A sample of polyamide was dissolved in m-cresol. Next, the sample was potentiometrically titrated with a 0.02N perchloric acid solution.
According to one embodiment of the invention, the polyamide has a total alkalinity strictly less than 35 μeq/g and a total acidity between 70 and 180 μeq/g.
Preferably, the polyamide has a total acidity of between 75 and 130. Mu. Eq/g. Preferably, the polyamide has a total basicity of less than or equal to 30 μeq/g and more particularly between 5 and 30 μeq/g.
According to one embodiment of the invention, the polyamide has a total acidity strictly less than 35. Mu. Eq/g and a total basicity between 60 and 180. Mu. Eq/g, preferably between 60 and 130. Mu. Eq/g.
Preferably, the polyamide has a total basicity of between 60 and 130. Mu. Eq/g. Preferably, the polyamide has a total acidity less than or equal to 30 μeq/g and more particularly between 5 and 25 μeq/g.
According to a preferred embodiment, the homo-polyamide according to the invention is PA11 or PA12, which has a total acidity of between 75 and 130 μeq/g and a total basicity of between 5 and 30 μeq/g.
Intrinsic viscosity
Preferably, the polyamide according to the invention has an intrinsic viscosity of between 0.70 and 1.70, advantageously between 0.70 and 1.50, preferably between 0.80 and 1.20, even more particularly between 0.85 and 1.15.
Intrinsic viscosity was measured by a viscometer equipped with a Micro-Ubbelohde viscometer tube at 20℃in a m-cresol solution at a polyamide concentration of 0.5% by weight relative to the total weight of the solution.
Crystallinity degree
Preferably, the polyamide has a crystallinity of between 20 and 40%, in particular between 20 and 30%, measured by DSC (differential scanning calorimetry) according to standard 11357-3,1999 (2 nd DSC heating at 20 ℃/min according to standard ISO 11357).
The crystallinity is calculated according to the formula:
Figure BDA0004113547260000061
wherein the method comprises the steps of
X is the degree of crystallinity of the glass,
ΔH f * Is the melting enthalpy of the polyamide,
ΔH f is the melting enthalpy of 100% crystalline polyamide. The value may be a theoretical value obtained by a mathematical model, or if a sample is available, it may be a value measured on the sample.
Chain stopper (chain stopper)
Advantageously, the polyamide according to the invention is limited (terminated) by a linear aliphatic C2-C18 monocarboxylic acid, a linear aliphatic C4-C18 monoamine, a linear aliphatic C3-C36 dicarboxylic acid and/or a linear aliphatic C4-C18 diamine.
The acid used as chain stopper may be selected from acetic acid, propionic acid, lactic acid, valeric acid, caproic acid, capric acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutyric acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, and docosanedioic acid.
Preferably, the polyamide according to the invention is limited by a linear aliphatic C6-C12 monocarboxylic acid and/or a linear aliphatic C6-C12 dicarboxylic acid, and particularly preferably by a linear aliphatic C6-C12 dicarboxylic acid. Preferred acids are adipic acid, sebacic acid and lauric acid.
The amine used as chain stopper may be selected from butylamine, hexylamine, octylamine, decylamine, laurylamine, stearylamine, diethylamine, dipropylamine, dibutylamine, hexamethylenediamine, heptylenediamine, octylamine, nonylenediamine, decylenediamine, undecylenediamine, dodecylamine.
Preferably, the polyamide according to the invention is limited by a C6-C12 monoamine and/or a C6-C12 diamine. Preferably, decamethylene diamine and laurylamine are used.
According to a particularly preferred embodiment of the invention, the polyamide is obtained by polycondensation of at least one linear aliphatic unit chosen from: a C6 to C12 α, ω -aminocarboxylic acid, a C6 to C12 lactam and a (Ca-diamine), (Cb-diacid) unit, wherein a represents the number of carbon atoms of the diamine and b represents the number of carbon atoms of the diacid, a and b being between 4 and 18, the polyamide having
A difference between 35 and 180 in absolute value between its total acidity and its total basicity,
-total basicity strictly less than 35 μeq/g, and
total acidity between 70 and 180 mueq/g,
the polyamide is limited by a mono-or di-acid.
Preferably, the polyamide is a homo-polyamide obtained by polycondensation of linear aliphatic units selected from the group consisting of C6 to C12 alpha, omega-amino carboxylic acids and C6 to C12 lactams, said polyamide having
A difference between 35 and 180 in absolute value between its total acidity and its total basicity,
-total basicity strictly less than 35 μeq/g, and
total acidity between 70 and 180 mueq/g,
the polyamide is limited by a mono-or di-acid.
Preparation method
The process for preparing the polyamide according to the invention comprises the step of mixing the monomers in the melt phase with at least one chain terminator, water and optionally further additives. This step is generally carried out at a temperature between 100 and 300 ℃ and at a pressure between 3 and 35 bar. This step may be performed in batch or continuous mode.
The water vapor is then removed by degassing and the pressure is reduced until atmospheric pressure is reached.
Finally, the polycondensation is continued under nitrogen or vacuum until the desired molecular weight is obtained.
The method may further comprise a subsequent filtration step to ensure that the polyamide is low in impurities. For example, the filtration step may be performed in an additional compounding step.
The addition of the additives may be carried out during the polymerization of the monomers or in a further compounding step.
Composition and method for producing the same
The invention also relates to a composition comprising a polyamide as defined hereinabove.
The composition may comprise at least one additive selected from the group consisting of: flame retardants, UV protectors, UV stabilizers, optical brighteners, heat stabilizers, pigments, lubricants, antioxidants, flow improvers, film formers, fillers, film forming aids, gums, semi-crystalline polymers, preservatives, antimicrobial agents, and mixtures thereof.
Preferably, the composition mainly comprises, i.e. comprises, at least 50% by weight and preferably between 70 and 90% of polyamide relative to the total weight of the polyamide composition.
According to a preferred embodiment, the composition according to the invention comprises the polyamide according to the invention and at most 10% by weight of at least one additive relative to the total weight of the composition.
According to a preferred embodiment, the composition according to the invention comprises PA11 or PA12 as the polyamide, the polyamide having
A difference between 35 and 180 in absolute value between its total acidity and its total basicity,
-total basicity strictly less than 35 μeq/g, and
total acidity between 70 and 180 mueq/g,
the polyamide is limited by a linear aliphatic C6-C12 dicarboxylic acid and preferably by adipic acid,
and having up to 10% by weight of at least one additive relative to the total weight of the composition.
According to a preferred embodiment, the composition according to the invention comprises PA11 or PA12 as the polyamide, the polyamide having
A difference between 35 and 180 in absolute value between its total acidity and its total basicity,
-total acidity strictly less than 35 μeq/g, and
total basicity between 60 and 180 mueq/g,
the polyamide is limited by linear aliphatic C6-C12 amines and preferably by decamethylene diamine and laurylamine,
and having up to 10% by weight of at least one additive relative to the total weight of the composition.
Use of the same
The polyamides according to the invention can be used for the manufacture of textile materials such as yarns, fibers, filaments, films, membranes, porous membranes, woven or nonwoven textiles. The invention also relates to the production of the molten polyamide particles and to the use thereof for adhering them to the surface of textile materials in a durable manner (wash-fastness).
The composition as defined hereinabove may also be used in the manufacture of textile materials such as yarns, fibers, filaments, films, membranes, porous membranes, woven or nonwoven textiles.
The polyamide or polyamide-based composition can be formed directly after polymerization into a textile material without an intermediate setting and remelting step. The polyamide or these compositions may also be formed into pellets for remelting for subsequent final forming, for example for the manufacture of molded textile articles or for the manufacture of yarns, fibers and/or filaments.
All melt spinning processes can be used in particular by passing the polyamide or the composition according to the invention through a spinneret comprising one or more holes. For the production of multifilament yarns, spinning or spin-draw-texturing processes (integrated or not) are possible, irrespective of the spinning speed. The yarn can be produced by spinning at high speeds of greater than or equal to 3000 m/min, preferably greater than or equal to 4000 m/min. These methods are generally expressed by the following terms: POY (partially oriented yarn), FOY (fully oriented yarn), ISD (integrated spin draft), HOY (highly oriented yarn at speeds greater than 5500 m/min). These yarns may also be textured according to their intended use. The yarns obtained by these processes are particularly suitable for the production of textiles, woven (knit) or knitted surfaces. According to the invention, thermoplastic polymer matrices made of the polyamide according to the invention can be used for the manufacture of monofilament yarns or monofilaments, multifilament yarns or multifilaments, continuous (bobbins) and/or discontinuous (short) fibers. The homopolyamide discontinuous fibers are particularly suitable for blending with natural fibers.
For single fibers or filaments, the denier can range from 1.5 dtex to 100 dtex per filament, with higher titers being particularly suitable for industrial applications. The multifilament yarns preferably have a titer of less than or equal to 6 dtex per filament. For the production of fibers, the filaments may be combined, for example, directly after spinning or during a re-spinning process, in the form of bundles (strands) or rolls (lap), drawn, textured or crimped and cut. The resulting fibers can be used to produce nonwoven or fibrous yarns. Polyamides or compositions may also be used to make flocs. The yarns, fibers and/or filaments of the present invention may be subjected to various treatments such as drawing, sizing, oiling, interlacing, texturing, crimping, drawing, sizing or relaxing heat treatment, milling, twisting and/or dyeing in a continuous or redraw step. For dyeing, bath or jet dyeing methods are mentioned in particular. Preferred dyes are acid, metallic and non-metallic dyes.
In one embodiment, the filaments of the polyamide of the invention have a strength of more than 3.5 cN/dtex, in particular more than 4 cN/dtex, in particular it is from 4 to 10 cN/dtex.
The invention also relates to filaments consisting of a polyamide as defined hereinabove or of a composition as defined hereinabove.
Textile product
The invention also relates to textiles made from the polyamide or the composition defined hereinabove.
The invention also relates to a textile (or textile article or textile material) obtained at least in part from the previously defined polyamide in the form of yarns, fibres and/or filaments as previously defined. These textile materials or articles may be fabrics or textile surfaces, such as woven, knitted, nonwoven or carpeted surfaces. Such articles may be, for example, carpets, rugs, upholstery, surface coverings such as sofa coverings, curtains, bedding, mattresses and pillows, apparel, and medical textile materials.
The textile according to the invention advantageously constitutes a felt, a filter, a membrane, a gauze, a cloth, a dressing, a layer, a fabric, a knitted fabric, an article of clothing, a garment, an article of bedding, an article of furniture, a curtain, an inner lining, a functional technical textile, a geotextile and/or an agricultural fabric.
The textile is advantageously used in the medical, hygiene, luggage, clothing, household or domestic equipment, furniture, carpeting, automobiles, industry, in particular industrial filtration, agriculture and/or in the construction field.
The invention also relates to a textile article obtained by: the polyamide matrix or thermoplastic composition comprising the polyamide according to the invention is shaped by extrusion methods, in particular by melt extrusion, in particular extrusion of sheets, films and filaments. Thus, a film can be obtained by the above method using a flat die. The resulting film may be subjected to one or more processing steps, such as one or two dimensional stretching, heat stabilization, antistatic treatment, and/or sizing.
When the textiles according to the invention are prepared mainly based on PA11 according to the invention (comprising at least 50 wt.% PA 11), then these textiles exhibit further advantageous properties. They are light, flexible, soft to the touch, tear, cut, abrasion and pilling resistant, and cool on the first touch.
Advantageously, the textile product also comprises natural fibres such as cotton, wool and/or silk, artificial fibres made from natural raw materials, metal fibres and/or synthetic fibres other than polyamide fibres according to the invention.
Advantageously, the textile comprises synthetic fibers obtained from bio-based raw materials. Preferably, the textile according to the invention is manufactured from only bio-based raw materials.
Renewable raw materials or biobased raw materials are materials that contain biobased carbon or carbon from renewable sources. In fact, unlike materials made from fossil fuels, materials made from renewable raw materials contain 14 C. "renewable carbon content" or "biobased carbon content" is determined according to ASTM D6866 (ASTM D6866-06) and, where applicable, ASTM D7026 (ASTM D7026-04). The first standard describes the following test: measuring the 14C/12C ratio of the sample and comparing it to a reference sample of 100% bio-based origin 14 C/ 12 The C ratios were compared to give the relative percentages of biobased C in the samples. The standard is based on 14 The same concept of the chronometry (dating) is applied but the chronometry formula is not applied. The ratio thus calculated is called "pMC" (modern carbon percentage). If the material to be analyzed is a mixture of biological and fossil materials (without radioisotopes), the pMC value obtained is directly related to the amount of biological material present in the sample. The ASTM D6866-06 standard proposes a variety of methods for measuring 14 Techniques for C isotope content based on LSC (liquid scintillation counting) or AMS/IRMS (accelerated mass spectrometry combined with isotope radiospectrometry). A preferred measurement method used in the context of the present invention is mass spectrometry as described in ASTM D6866-06 ("accelerator mass spectrometry").
The inventive textile product comprising the inventive polyamide 11 is at least partly derived from biobased raw materials and thus has a biobased carbon content of at least 1%, which corresponds to at least 1.2x10 -14 A kind of electronic device 12 C/ 14 C isotope ratio. Preferably, the textile according to the invention comprises at least 50 mass% bio-based carbon relative to the total mass of carbon, which corresponds to at least 0.6.10 -12 A kind of electronic device 12 C/ 14 C isotope ratio. This content is advantageously higher, in particular up to 100%, which corresponds to 1.2x10 -12 A kind of electronic device 12 C/ 14 C isotope ratio. Thus, the textile according to the invention may comprise 100% bio-based carbon or, alternatively, be produced from a mixture with fossil sources.
According to a preferred embodiment, the textile according to the invention is made of PA11 or PA12, the polyamide having
A difference between 35 and 180 in absolute value between its total acidity and its total basicity,
-total basicity strictly less than 35 μeq/g, and
total acidity between 70 and 180 mueq/g,
the polyamide is limited by a linear aliphatic C6-C12 dicarboxylic acid and preferably by adipic acid.
According to another preferred embodiment, the textile according to the invention is made of a composition comprising PA11 or PA12, said polyamide having
-the difference between its total acidity and its total basicity expressed in absolute value between 35 and 180, and
-total acidity strictly less than 35 μeq/g, and
total basicity between 60 and 180 mueq/g,
the polyamide being limited by aliphatic linear amines, and
having up to 10% by weight of at least one additive relative to the total weight of the composition.
Other objects and advantages of the present invention will become apparent from the following examples, which are not intended to be limiting.
Examples
Examples: sample preparation
The polyamide according to the invention, denoted a, is PA11 limited by adipic acid (C6 diacid) in a proportion of 0.67% by weight relative to the amount of 11-aminoundecanoic acid added.
The polyamide is prepared according to the following method. 11-aminoundecanoic acid, water and adipic acid were added to the reactor, and then placed in an inert atmosphere. The reaction medium was then heated to 235 ℃ while maintaining agitation. The reaction medium is maintained at 235℃and a pressure of 20 bar for 1.5 hours. The pressure was then reduced to 12 bar while maintaining the temperature at 235 ℃. The material was then transferred to a polymerizer at 235 ℃ under a nitrogen purge. The temperature was maintained for 1.5 hours under a nitrogen purge. The material is then extruded in the form of pellets. This method was used for all example polyamides.
The polyamide according to the invention, denoted B, is PA11 limited by lauric acid (C12 monoacid) in a proportion of 1.10% by weight relative to the amount of 11-aminoundecanoic acid added.
The polyamide according to the invention, denoted C, is PA11 limited by laurylamine (C12 monoamine) in a proportion of 0.83% by weight relative to the amount of 11-aminoundecanoic acid added.
The polyamide according to the invention, denoted D, is PA11 limited by decanediamine (C10 diamine) in a proportion of 0.80% by weight relative to the amount of 11-aminoundecanoic acid added.
The polyamide according to the invention, denoted E, is PA1010 limited by sebacic acid, the excess ratio of sebacic acid being added being 0.90% by weight relative to the sum of the stoichiometric amounts of decanediamine and sebacic acid.
The comparative polyamide denoted F is a polyamide obtained by Arkema France under the trade name
Figure BDA0004113547260000121
BMNO sells PA11.
The comparative polyamide denoted G is a polyamide obtained by Arkema France under the trade name
Figure BDA0004113547260000122
KNO sells PA11.
The polyamide denoted H is a polyamide obtained by Arkema France under the trade name
Figure BDA0004113547260000123
PA12 sold by AECNO.
Measurement of intrinsic viscosity
Intrinsic viscosity was measured by a viscometer equipped with a Micro-Ubbelohde viscometer tube at 20℃in a m-cresol solution at a polyamide concentration of 0.5% by weight relative to the total weight of the solution.
Measurement of Total acidity
Acidity was measured according to the following method. 1g of polyamide was dissolved in 80mL of benzyl alcohol with heat. The sample was then cooled. It was then potentiometrically titrated with 0.02N tetrabutylammonium hydroxide solution using a Metrohm titrator (888 or 716) with a combined pH electrode. The potential versus volume curve gives the jump in equivalent volume from which the total acidity is calculated using the following formula:
Figure BDA0004113547260000131
wherein the method comprises the steps of
Veq is the equivalent volume obtained by potentiometric titration,
the [ TBAOH ] is the concentration of the tetrabutylammonium hydroxide solution, i.e., 0.02N,
m is the mass of the sample, i.e. 1g.
Measurement of Total alkalinity
Alkalinity was measured according to the following method. 1g of polyamide was dissolved in 80mL of hot meta-cresol. The sample was then cooled. It was then potentiometrically titrated with a 0.02N perchloric acid solution in acetic acid using a Metrohm titrator (888 or 716) with a combined pH electrode. The potential versus volume curve gives the jump in equivalent volume from which the total alkalinity is calculated using the following formula:
Figure BDA0004113547260000132
wherein the method comprises the steps of
Veq is the equivalent volume obtained by potentiometric titration,
[ HClO4] is the concentration of the perchloric acid solution, i.e., 0.02N,
m is the mass of the sample, i.e. 1g.
Calculation of the difference between Total acidity and Total basicity
The difference is obtained in absolute value (i.e. without taking the sign into account) by subtracting the total acidity and the total basicity from each other.
For example, for PA 11A:
Δ＝|103-18|＝85
the total alkalinity and total acidity values of the polyamides tested were as follows:
Figure BDA0004113547260000133
Figure BDA0004113547260000141
example 2: analysis of thermal stability
The polyamides according to the invention and the comparative polyamides were analyzed for their thermal stability upon heating.
Melt viscosity was evaluated under the following conditions:
the device comprises: PHYSICA MCR301 and 301
Geometry: parallel planes of diameter 25mm
Temperature: 220 ℃ and 240 DEG C
Frequency: 10rad. S -1
Deformation: 5%
Duration of time: 30 minutes
Atmosphere: and (5) flushing with nitrogen.
These conditions are those of standard ISO 6721-10:1999.
The results with respect to viscosity at 220 ℃ are reported in table 2 below:
Figure BDA0004113547260000142
the results with respect to viscosity at 240 ℃ are reported in table 3 below:
Figure BDA0004113547260000143
these results show that the polyamide according to the invention changes very little when heated. Its viscosity is virtually constant over time; this is in contrast to the comparative polyamide, which is observed to increase significantly in viscosity over time at 220℃and 240 ℃.
These results show that the polyamide according to the invention is perfectly recyclable.
Example 3: analysis of Heat resistance
The heat resistance of the polyamide according to the invention and the comparative polyamide was analyzed.
The heat resistance was evaluated under the following conditions. Measurements were carried out on a Netzsch TG 209F1 instrument at 10℃per minute from 25 to 550℃under air and under nitrogen.
The results are shown in table 4 below:
Figure BDA0004113547260000151
these results show that the polyamide according to the invention has better heat resistance both under air and under nitrogen.
These results indicate that filaments made from the polyamide according to the invention will have better mechanical properties, since they are much less sensitive to temperature.
Example 4: analysis of elongation Properties
Dumbbell shaped specimens were prepared from polyamide granules according to standard ISO 527 1 a.
Tensile testing was performed at 23 ℃ according to standard ISO 527 1a: 2012. The test involves applying mechanical stress to the dumbbell specimen. The percentage of maximum elongation of the dumbbell specimen was measured before the second threshold.
The results are shown in table 5 below:
Figure BDA0004113547260000152
these results show that the polyamide according to the invention has better mechanical properties at room temperature than those obtained with the comparative polyamide, which does not satisfy the characteristics of total alkalinity and total acidity. From these results, it can be concluded that the filaments obtained from the polyamide according to the invention have better stretchability and strength.
Example 5: characterization of the Strength of Polyamide filaments according to the invention
Filaments are prepared from polyamide PA 11A according to the invention. The strength of the filaments was measured according to standard ISO 2062 at a speed of 250 mm/min and a distance of 250mm between the two jaws.
For an elongation of 22%, a value of 4.4 cN/dtex is obtained.
Thus, fabrics made with the polyamide according to the invention can be used in the field of sports.
Example 6: spinning method
The PA 11A according to the invention and the comparative PA 11F were evaluated in a multifilament extrusion. The system used is characterized in that:
and (3) an extruder: 19mm (3/4') 30:1L/D
And (3) a pump: 0.6 cc/rev
Spinning head assembly: 36 wells, L/d=4; l=1.4 mm and d=0.35 mm
Temperature profile in degrees celsius:
Figure BDA0004113547260000161
the PA 11A according to the invention makes it possible to obtain multifilaments without difficulty, due to its flowability and its rheological stability. The process is stable, has no filament breakage, and has excellent yields.
However, for comparative PA 11F, the method is unstable. We observed that a more viscous material formed at the exit of the spinneret, resulting in a multifilament break. In fact, due to its reactivity in the melt phase, the viscosity of the comparative PA 11F varies during the spinning process and therefore continuous adjustment of the extrusion parameters is required to overcome this problem. However, from an industrial point of view, this is not feasible.
Thus, the comparative PA 11F is not suitable for the production of multifilament yarns, whereas the formulation of PA 11A according to the invention is particularly suitable for this type of conversion process.

Claims (12)

1. Linear aliphatic polyamide obtained by polycondensation of at least one linear aliphatic unit selected from the group consisting of: a C6 to C12 alpha, omega-aminocarboxylic acid, a C6 to C12 lactam and a (Ca-diamine), (Cb-diacid) unit, wherein a represents the number of carbon atoms of the diamine and b represents the number of carbon atoms of the diacid, a and b being between 4 and 18,
the polyamide has
-the difference between its total acidity and its total basicity expressed in absolute value between 35 and 180, and
total basicity or total acidity strictly less than 35 μeq/g.
2. Polyamide according to claim 1, characterized in that it has an intrinsic viscosity comprised between 0.70 and 1.70, advantageously comprised between 0.70 and 1.50, preferably comprised between 0.80 and 1.20, even more particularly comprised between 0.85 and 1.15.
3. Polyamide according to claim 1 or 2, characterized in that it is a homo-polyamide.
4. A polyamide according to claim 3, characterized in that it is obtained by polycondensation of linear aliphatic units selected from the group consisting of: a C8 to C12 α, ω -aminocarboxylic acid, a C8 to C12 lactam and a (Ca-diamine), (Cb-diacid) unit, wherein a represents the number of carbon atoms of the diamine and b represents the number of carbons of the diacid, a and b being between 8 and 12.
5. Polyamide according to claim 4, characterized in that it is PA11, PA12, PA1010, PA1012.
6. Polyamide according to any one of claims 1 to 5, characterized in that when the total alkalinity is strictly less than 35 μeq/g then the total acidity is between 70 and 180 μeq/g or when the total acidity is strictly less than 35 μeq/g then the total alkalinity is between 60 and 180 μeq/g.
7. Polyamide according to any one of claims 1 to 6, characterized in that it is limited by a linear aliphatic C2-C18 monocarboxylic acid, a linear aliphatic C4-C18 monoamine, a linear aliphatic C3-C36 dicarboxylic acid and/or a linear aliphatic C4-C18 diamine.
8. Process for the preparation of a polyamide as defined in any one of claims 1 to 7, characterized in that it comprises:
a step of mixing the monomers in the melt phase with at least one chain terminator, water,
-optionally, a step of filtering the mixture obtained in the previous step.
9. Composition essentially comprising a polyamide as defined in any one of claims 1 to 7 and at least one additive selected from the group consisting of: flame retardants, UV protectors, UV stabilizers, optical brighteners, heat stabilizers, pigments, lubricants, antioxidants, flow improvers, film formers, fillers, film forming aids, gums, semi-crystalline polymers, preservatives, antimicrobial agents, and mixtures thereof.
10. Use of a polyamide as defined in any one of claims 1 to 7 or a composition as defined in claim 9 for the manufacture of a textile material.
11. Filaments consisting of a polyamide as defined in any one of claims 1 to 7 or a composition as defined in claim 9.
12. Textile, characterized in that it comprises a polyamide as defined in any one of claims 1 to 7 or a composition as defined in claim 9.
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